The determination of the stoichiometric ratio in the molecular association system is of great signification. The asynchronous orthogonal sample design scheme @ Job’s (AOSD@Job’s) method, which was developed in our previous work, had a considerable advantage over the commonly-used Job’s method. However, the AOSD@Job’s method might give incorrect results due to the severe interference of the noise from the spectral measurements . In this paper, a modified AOSD@Job’s (MAOSD@Job’s) method was proposed by introducing the modified reference spectrum into the AOSD@Job’s method. Firstly, mathematical analysis suggested that the MAOSD@Job’s method might be more robust to noise compared with the AOSD@Job’s method. Then, the results of computer simulation showed that the stoichiometric ratios obtained from the MAOSD@Job’s method were all consistent with the set values under the disturbance of noise. However, AOSD@Job’s method produced incorrect stoichiometric ratios in the computer simulation experiments due to the interference of noise. Lastly, the MAOSD@Job’s method was successfully applied on two real chemical systems.
Min Shao,Muhan Chen,Mei Fan,Guoting Luo,Ci Jin,Zhangjie Huang
In this study, based on a cyano-functionalized ionic liquid, 1-nitrile-1-octylpyrrole bromide ([C 8 Y 3 Pr]Br), a [C 8 Y 3 Pr]Br/cyclohexane/tributyl phosphate (TBP)/NaCl microemulsion system was constructed and used for the extraction of Pd(II) and preparation of Pd nanoparticles from multimetal solutions. The key extraction parameters including vibration time, [C 8 Y 3 Pr]Br concentration, phase ratio ( R W/O ), and HCl concentration were evaluated. Compared with other ionic-liquid microemulsion systems, the cyano-functionalized ionic liquid [C 8 Y 3 Pr]Br microemulsion system showed excellent extraction performance for Pd(II). Almost all Pd(II) was extracted (>98.0%) from a multimetal solution using the microemulsion system, while the separation factors ( β Pd/M ) of [C 8 Y 3 Pr]Br-based microemulsions for Pd(II) with Cu 2+ , Fe 3+ , Ni 2+ , Zn 2+ , Co 2+ , and Mg 2+ exceeded 1.0 × 10 3 . The mechanism extracting Pd(II) using [C 8 Y 3 Pr]Br was confirmed to be an anion-exchange reaction via Job’s method, spectral analysis (UV, FTIR), and DFT calculations. Alcohols and hydrazine hydrate were used as demulsifiers, and Pd nanoparticles were directly obtained from the microemulsion phase. The Pd nanoparticles were identified by TEM, XPS, and XRD analyses. The chemical structures of extracted species based on the microemulsion system and the mechanism of demulsification of alcohols were studied. Thus, an effective new process was developed in this study for the direct preparation of Pd nanoparticles from mixed metal solutions via solvent extraction.
危险品化学品经营许可证（带存储）